Layered minerals and compositions comprising the same

ABSTRACT

Novel silicate minerals that have undergone a cation exchange with at least one heteroaromatic cation comprising a positively charged organo-substituted heteroatom and/or at least one positively charged heteroatom not part of an aromatic ring with at least one bond having a bond order greater than one and compositions comprising the same are described.

FIELD OF THE INVENTION

This invention relates to novel silicate minerals as well ascompositions comprising the same. More particularly, the instantinvention relates to layered minerals that have undergone a cationexchange with at least one heteroaromatic cation comprising a positivelycharged organo-substituted heteroatom and/or at least one positivelycharged heteroatom not part of an aromatic ring with at least one bondhaving a bond order greater than one.

BACKGROUND OF THE INVENTION

Compositions comprising polycarbonates, polyesters and polyphenyleneethers, for instance, constitute invaluable classes of engineeringthermoplastics. They are characterized by a unique combination ofchemical, physical and electrical properties. For example, they arechemically stable and generally display high impact strengths.

It is of increasing interest to prepare polymer compositions that, whileretaining their characteristic properties, have higher heat deflectiontemperatures. Particularly, there is demand for polycarbonate, polyesterand polyphenylene ether compositions which possess increased heatdeflection temperatures since they are, for instance, conventionallyused in commercial applications often exposed to elevated temperatures.Moreover, fillers, for example, have been added to polymer compositionsin an attempt to improve properties.

The instant invention therefore is based on the discovery of novellayered minerals which may be employed as components of compositions andnovel compositions prepared from low viscosity macrocyclic oligomers.

DESCRIPTION OF THE PRIOR ART

Efforts have been disclosed for preparing polymeric nanocomposites. InInternational Application WO 94/11430, nanocomposites having twoessential components are described and the two essential components aregamma phase polyamides and layered and fibrillar inorganic materialswhich are treated with quaternary ammonium cations.

Still other efforts have been made to prepare composite materialscontaining a layered silicate. In U.S. Pat. No. 4,889,885, a compositematerial having high mechanical strength and heat resistance which issuitable for use in automotive parts, aircraft parts and buildingmaterials is described.

The instant invention is patentably distinguishable from the,above-described since, among other reasons, it is directed to novellayered minerals that have undergone a cation exchange with at least oneheteroaromatic cation comprising a positively charged organo-substitutedheteroatom and/or a positively charged heteroatom not part of anaromatic ring with at least one bond having a bond order greater thanone, and compositions prepared therefrom. Additionally, the instantinvention is directed to novel compositions prepared from low viscositymacrocyclic oligomers.

SUMMARY OF THE INVENTION

In a first aspect, this invention is directed to novel layered mineralsthat have undergone a cation exchange with at least one member selectedfrom the group consisting of:

(a) a heteroaromatic cation comprising at least one positively chargedorgano-substituted heteroatom; and

(b) a cation comprising at least one positively charged heteroatom notpart of an aromatic ring with at least one bond having a bond ordergreater than one.

In a second aspect, the instant invention is directed to compositionswhich comprise at least one organic system, either macrocyclic and/orlinear and/or branched polymer, and the aforementioned layered mineralshaving undergone a cation exchange with at least one of the cationsdescribed in (a) and (b).

In a third aspect, the instant invention is directed to compositionswhich comprise macrocyclic oligomers and layered minerals that haveundergone a cation exchange with onium compounds.

In a fourth aspect, the instant invention is directed to a process forproducing polymers by polymerizing macrocyclic oligomers in the presenceof layered minerals.

In a fifth aspect, the instant invention is directed to thepolymerization product of the macrocyclic oligomer compositions.

It is often preferred that the compositions described herein comprisethe layered minerals that have undergone a cation exchange with thecations described in (a) and (b) since such compositions unexpectedlydisplay an improvement in their rigidity as depicted by an increase intheir elastic modulus and/or an improvement in their stability asdepicted by their molecular weights. Moreover, subsequent to blendingpolymer and layered minerals the compositions may be referred to asnanocomposites which are defined herein as a composition having anorganic system and a layered mineral (clay) component dispersed thereinand the layered mineral has at least one dimension which is nanometerscale in size.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

There is no limitation with respect to the layered minerals employed inthis invention other than that they are capable of undergoing a cationexchange with the cations and/or onium compounds mentioned above.Illustrative of such layered minerals that may be employed in thisinvention include, for instance, those of the kaolinite group and themontmorillonite group. The former group can include kaolinite,halloysite, dickite, nacrite and the like. The latter group can includemontmorillonite, nontronite, beidellite, hectorite, saponite and thelike.

It is also within the scope of the invention to employ minerals of theillite group which can include hydromicas, phengite, brammallite,glaucomite, celadonite and the like. Moreover, layered mineralsincluding kenyaite, magadite, muscovite, sauconite, vermiculite,volkonskoite as well as any minerals classified as phyrophyllics, micasor smectites may be employed in this invention; again, with the provisothat they are capable of cation exchanging as mentioned above.

Still further, it is within the scope of the instant invention toinclude layered minerals which are classified as layered doublehydroxides as well as layered minerals having little or no charge ontheir layers provided that they are capable of expanding when contactedwith the cations and onium compounds mentioned above.

Often, however, the preferred layered minerals include those oftenreferred to as 2:1 layered silicate minerals like muscovite,vermiculite, beidelite, saponite, hectorite and montmorillonite, whereinmontmorillonite is often preferred.

In addition to the clays mentioned above, admixtures prepared therefrommay also be employed as well as accessory minerals including, forinstance, quartz, biotite, limonite, hydrous micas, feldspar and thelike.

The layered minerals described above may be synthetically produced.However, most often they are naturally occurring and commerciallyavailable. They are typically prepared via a number of methods whichinclude the hydrolysis and hydration of silicates, shale weathering aswell as the action of acid clays, humus and inorganic acids on primarysilicates.

Cation, as used herein, is defined, for instance, as being positivelycharged compounds derived from heteroaliphatic, heteroalicyclic orsubstituted or unsubstituted heteroaromatic compounds, includingmonocyclic, bicyclic, tricyclic and polycyclic compounds.

There is no limitation in this invention with respect to theheteroaromatic cations comprising at least one positively chargedorgano-substituted heteroatom or the cations comprising at least onepositively charged heteroatom not part of an aromatic ring with at leastone bond having a bond order greater than one. Bond order greater thanone is defined herein as any bond greater than a single bond includingpartial double bonds and double bonds. The only proviso is that they arecapable of undergoing a cation exchange with the layered mineralsemployed in this invention.

The heteroaromatic cations employed in this invention may be substitutedor unsubstituted on atoms aside from the organo-substituted heteroatoms,and they can contain more than one heteroatom. Therefore, it is withinthe scope of the instant invention to include cations derived from, forinstance, C₃₋₁₄ aromatics including benzene, naphthalene, anthracene orphenanthrene and the like and "derived from" as used throughout is meantto mean that at least one skeletal carbon atom is replaced with at leastone heteroatom.

The latter cations comprising at least one positively charged atom withat least one bond having a bond order greater than one include, forinstance, imines (Schiff bases) and any inium cations derived therefromsuch as aza, thia, phospha and oxa containing cations. Therefore, theheteroaromatic cations comprising at least one positively chargedorgano-substituted heteroatom and the cations comprising at least onepositively charged atom not part of an aromatic ring with at least onebond having a bond order greater than one can be referred to herein asinium-type cations since they are trigonally planar in nature anddistinguishable from onium-type cations which are tetrahedral in nature.

There is no limitation with respect to the heteroatom employed in thisinvention and they are often selected from the group consisting of N, P,O and S and preferably N.

Often preferred heteroaromatic cations that comprise at least onepositively charged organo-substituted heteroatom employed in thisinvention include, for example, N-organo-substituted salts of pyrrole,imidazole, thiazole, oxazole, pyridine, pyrimidine, quinoline,isoquinoline, indole, purine, benzimidazole, benzothiazole, benzoxazole,pyrazine, quinoxaline, quinazoline, acridine, phenazine,imidazopyridine, dipyridyl and the like.

The organo-substituent on the organo-substituted heteroatom is often aC₁₋₂₅ aliphatic, alicyclic or aromatic group and preferably a C₁₋₁₈group, and the often most preferred cations are N-C₁₀₋₁₈ pyridiniumcations. An illustrative list includes, for instance,N-dodecylpyridinium cations, N,N'-ditetradecylbenzimidazolinium cationsand 4-(dialkylamino)-N-alkylpyridinium cations like4-(dibutylamino)-N-butylpyridinium cations and the like.

The cations comprising at least one heteroatom with at least one bondhaving a bond order greater than one often include, for example, thosehaving the formula ##STR1## wherein R¹, R², R³ and R⁴ are eachindependently a hydrogen, ##STR2## C₁₋₂₀ alkyl group, aromatic radical,substituted heteroatom or R⁵ and R⁵ is hydrogen or a C₁₋₁₀ alkyl group,or at least one of R¹ and R², R³ and R⁴, R¹ and R³ and R² and R⁴ takentogether with the atoms connecting them can form a 4 to 10 memberedcyclic or bicyclic ring. Often preferred cations employed in thisinvention include salts of guanidines and amidines; therefore,guanadinium and amidinium type cations. Illustrative examples includehexaalkylguanidinium salts like N,N,N',N',N",N"-hexabutylguanidiniumcations as well as those described in U.S. Pat. No. 5,132,423, thedisclosure of which is incorporated herein by reference.

Other cations which comprise at least one heteroatom with at least onebond having a bond order greater than one include, for instance, thosederived from C₁₋₁₄ heteroalicycloalkenes like bicyclododecene,bicyclononene, bicycloundecene, tricyclotetradecene and the like as wellas those that may be derived from bicyclo and spirobicyclo compounds.

When compositions are prepared with macrocyclic oligomers, layeredminerals having undergone a cation exchange with onium type compoundsmay be employed. Such onium type compounds include ammonium, phosphoniumand sulfonium type salts such as those having the formula ##STR3##wherein each R⁶ is independently a hydrogen, C₁₋₂₀ alkyl group orsubstituted or unsubstituted aromatic radical or two R⁶ s together withatoms connecting them can form a 4 to 12 membered cyclic or bicyclicring and X is N, P or S and y is an anion and often CI or Br. It is alsowithin the scope of the instant invention for at least one R⁶ tocomprise reactive functionalized groups such as unsaturated carbongroups, carbonyl groups including carboxylic acid derivatives andnitrogen containing derivatives such as amines and the like as well asepoxy groups, orthoester groups and the like.

Other onium type cations which may be employed include, for example,salts of pyrrolidine, piperidine, piperazine and morpholine as well asheterocations derived from bicyclododecane, bicyclononane,bicycloundecane, tricycloundecane and the like.

The compositions of this invention comprising layered minerals havingundergone a cation exchange with at least one heteroaromatic cationcomprising a positively charged organo-substituted heteroatom and/or atleast one positively charged heteroatom not part of an aromatic ringwith at least one bond having a bond order greater than one alsocomprise organic systems which are defined as any polymers or oligomerscapable of being combined with the layered minerals. Often such organicsystems include macrocyclic oligomers as well as linear and branchedpolymers. There is no limitation with respect to the organic systemsemployed in this invention and they are commercially known andconventionally produced. They can often comprise those selected from thegroup consisting of linear and branched polymers of polycarbonates,polyesters, polyphenylene ethers, polyimides, olefins, polyetherimides,polyamides, polyarylene sulfides, polysulfones, polyetherketones,acrylonitrile butadiene styrene copolymers, polystyrenes and blends,compositions or copolymers prepared therefrom.

Still further, the organic systems employed in this invention may oftencomprise macrocyclic oligomers selected from the group consisting ofmacrocyclic polycarbonates, polyesters, polyimides, polyetherimides,polyphenylene ether-polycarbonate co-oligomers,polyetherimide-polycarbonate co-oligomers and blends, compositions andco-oligomers prepared therefrom. Moreover, organic systems comprisingpolyesters, polycarbonates or polyphenylene ethers are often preferred.Such organic systems typically include, for example, polyesters likepoly(1,2-ethylene terephthalate), poly(1,4-butylene terephthalate),poly(1,2-ethylene 2,6',-naphthalenedicarboxylate) and the like andco-polymers thereof and polycarbonates like bisphenol A polycarbonateand the like and polyphenylene ethers including homopolymers containing2,6-dimethyl-1,4-phenylene ether units or 2,3,6-trimethyl-1,4-phenyleneether units as well as copolymers thereof. It is also noted herein thatall of the organic systems may be unfunctionalized or functionalized byany of the well known methods described in the art including acid,anhydride and orthoester type functionalizations common in the art.

The layered minerals of the instant invention typically possessnegatively charged layers having intercalated inorganic alkali and/oralkaline earth cations present therein. The result of such is a strongelectrostatic interaction between the charged layers and the cations,rendering the layered minerals often difficult to disperse in non-polarorganic systems. In the instant invention, the layered minerals areprepared, for instance, by subjecting them to the cations comprising apositively charged organo-substituted heteroatom and/or at least onepositively charged heteroatom not part of an aromatic ring with at leastone bond having a bond order greater than one in a homogeneousdispersion usually comprising water and a water miscible organic solventincluding alcohols and ketones. Such preparation renders the layeredminerals less difficult to disperse in non-polar organic systems.

Compositions comprising the layered minerals may be prepared, forexample, by melt blending/extruding the layered minerals with polymer ormixing the layered minerals in low viscosity macrocyclic oligomers priorto polymerizing, wherein low viscosity is defined as being less thanabout 2,000 centipoise. When the layered minerals are mixed in a lowviscosity macrocyclic oligomer, polymer is subsequently formed usuallyby adding an appropriate catalyst such as, for example, a zinc, titaniumor tin containing polymerization catalyst. Moreover, the compositionscomprising the layered minerals in the instant invention are often nomore than about 70% by weight and preferably no more than about 40% byweight and most preferably no more than about 20% by weight layeredmineral based on total weight of the composition.

The following examples further illustrate and facilitate theunderstanding of the instant invention. The products obtained may beconfirmed by conventional techniques such as proton and carbon 13nuclear magnetic resonance spectroscopy and GPC analysis.

EXAMPLE 1

A mixing blender was charged with 500 mL of water, 200 mL of methanoland 11 g of sodium montmorillonite (10% H₂ O 119 meq/100 g) which wasadded in portions to produce a homogeneous dispersion. The homogeneousdispersion was vigorously stirred and a solution of dodecylammoniumchloride consisting of 4.85 g (26.2 mmol) of the amine, 2.64 g of 37%aqueous HCl, 25 mL of H₂ O and 25 mL of methanol, was added all at onceto the dispersion. A white precipitate was produced and recovered byfiltration and subsequently washed with water. The resulting washedprecipitate was re-dispersed in 700 mL of H₂ O. The resulting washedprecipitate (montmorillonite having undergone a cation exchange with anammonium cation) was recovered (12.12 g) by filtration and freeze-driedunder vacuum.

EXAMPLE 2

In Example 2, layered mineral was prepared in a manner similar to theone described in Example 1 except that N-hexadecylpyridinium chloridewas employed in lieu of dodecylammonium chloride. Recovered wasmontmorillonite having undergone a cation exchange with a cationcomprising a positively charged organo-substituted heteroatom.

EXAMPLES 3 AND 4

Macrocyclic oligomer compositions were prepared by charging two mixingflasks, both with 4.8 g macrocyclic oligomer (cyclic terephthalateco-oligomer 5:95 mixture of ethylene and butylene glycols, based ontotal weight of the co-oligomer)) and one (Example 3) withmontmorillonite (0.20 g) having undergone a cation exchange as describedin Example 1 and the other (Example 4) with montmorillonite (0.20 g)having undergone a cation exchange as described in Example 2. Theresulting mixtures were flushed with nitrogen and then dried under avacuum of 0.05 torr at 110° C. for 0.5 hour. The flasks were then placedin an oil bath maintained at 190° C. to melt the mixtures under vacuum.The resultant low viscosity translucent liquids were stirred for 15minutes at 190° C. to produce macrocyclic oligomer melt compositions.Subsequent to cooling, the compositions solidified having layeredminerals homogeneously dispersed therein.

EXAMPLE 5

A polymerization catalyst, dioctyltin dioctoxide (62 μl, 0.109 mmol) wasadded at 190° C. to a macrocyclic oligomer melt composition as preparedin Example 4, to polymerize the oligomers. The melt became viscous inabout 15 seconds and the resulting solid polymer composition comprisingmontmorillonite having undergone cation exchange formed in about 2minutes. The weight average molecular weight (Mw) determined by gelpermeation chromatography (GPC) of the polymerized composition obtainedwas 103,000.

EXAMPLE 6

A composition was prepared in a manner similar to the one described inExample 5 except that a cyclic butylene terephthalate homo-oligomer wasemployed in lieu of cyclic terephthalate co-oligomer composed of 5:95mixture of ethylene and butylene glycols, and dioctyl2,2-diethyl-1,3-propylenedioxytitanate was employed as a polymerizationcatalyst in lieu of dioctyltin dioctoxide. The weight average molecularweight of the polymerized composition obtained was 145,000.

EXAMPLE 7

The composition in this example was prepared in a manner similar to theone described in Example 6 except that montmorillonite as prepared inExample 2 was employed in lieu of montmorillonite as prepared in Example1 and tetraoctyl titanate, a polymerization catalyst was used in lieu ofdioctyl 2,2-diethyl-1,3-propylenedioxytitanate. The weight averagemolecular weight was 139,000.

EXAMPLE 8

A well mixed dry blend of polyphenylene ether (homopolymer containing2,6-dimethyl-1,4-phenylene ether units) (20 parts) and montmorilloniteas prepared in Example 2 (1 part) was extruded using a twin screwextruder operating at 295° C. and 400 rpm with a feed rate ofapproximately 40 g/minute. The extrudate was pelletized, dried at 90° C.in a vacuum oven and test specimens were injection molded on a 15 toninjection molder at 310° C. The compositions exhibited a shear modulusof 13.9×10⁹ dyne/cm² at room temperature which is a 29% increase overthe compositions produced using unmodified montmorillonite. Compositionsproduced using an onium salt modified montmorillonite resulted in only15% improvement in modulus.

EXAMPLE 9

The composition in this example was prepared in a manner similar to theone described in Example 8 except that poly(1,4-butylene terephthalate)powder was employed in lieu of polyphenylene ether and the extrudertemperature was about 260° C. The resulting extrudate was pelletized,dried in an air circulating oven at 120° C. for 4 hours and molded on a30 ton injection molding machine. The composition had a weight averagemolecular weight of 97.2×10³ whereas compositions prepared by usingdodecylammonium cation modified layered minerals had a weight averagemolecular weight of 84.6×10³.

The data in the tables below is provided to demonstrate the unexpectedand superior properties obtained in the instant invention. All entrieshave been prepared in a manner similar to those described in theexamples.

                  TABLE I                                                         ______________________________________                                               Organic  Layered                Shear                                  Entry  System.sup.a                                                                           mineral.sup.b                                                                           Cation.sup.c                                                                        T °C.                                                                         Modulus.sup.d                          ______________________________________                                        1      PBT      None      None   60    4.59                                                                   150    0.86                                                                   200    0.51                                   2      PBT      M         Na+    60    5.74                                                                   150    1.13                                                                   200    0.666                                  3      PBT      m         Na+    60    7.88                                                                   200    0.87                                   4      c-PBT    M'        DDA    60    6.80                                                                   150    1.79                                                                   200    0.82                                   5      PBT      M         DDA    60    9.04                                   6      PBT      m         DDA    60    15.6                                   7      PBT      M         DDA   200    0.88                                   8      PBT      m         DDA   200    1.38                                   9      PBT      M         HDA    60    9.8                                                                    200    0.97                                   10     PBT      M         HDP    60    8.27                                                                   200    0.85                                   11     PPE      None      None   25    10.2                                   12     PPE      M         Na+    25    10.8                                   13     PPE      M         HDA    25    12.4                                   14     PPE      M         HDP    25    13.9                                   ______________________________________                                         .sup.a PBT =  poly(1,4butylene terephthalate); cPBT = in situ polymer fro     ringopening polymerization of macrocyclic butylene terephthalate              oligomers; PPE = polyphenylene ether.                                         .sup.b M = montmorillonite, 5% of the total weight of the organic system.     m = montmorillonite, 15% of the total weight of the organic system; M' =      4% of the total weight of the organic system.                                 .sup.c Na+ = control; DDA = dodecylammonium cation; HDA =                     hexadecylammonium cation; HDP = Nhexadecylpyridinium cation.                  .sup.d (10.sup.9 dyne/cm.sup.2).                                         

                  TABLE II                                                        ______________________________________                                        Entry Organic System.sup.e                                                                       Layered mineral.sup.f                                                                      Cation.sup.g                                                                        MW.sup.h                                ______________________________________                                        1     PPE          None         None  74.0                                    2     PPE          M            Na+   72.9                                    3     PPE          M            DDA   61.9                                    4     PPE          M            TDA   67.6                                    5     PPE          M            HDA   62.2                                    6     PPE          M            TDP   65.2                                    7     PPE          M            HDP   67.0                                    8     PBT          None         None  104.0                                   9     PBT          M            Na+   94.9                                    10    PBT          m            Na+   92.9                                    11    PBT          M            DDA   84.6                                    12    PBT          m            DDA   74.3                                    13    PBT          M            HDP   97.2                                    ______________________________________                                         .sup.e As defined in Table I.                                                 .sup.f As defined in Table I.                                                 .sup.g As defined in Table I and TDP = Ntetradecylpyridinium; Na+ =           control.                                                                      .sup.h Weight average molecular weight × 10.sup.-3.                

What is claimed is:
 1. A composition comprising:(a) a layered mineralhaving undergone a cation exchange with at least one member selectedfrom the group consisting of:(i) a heteroaromatic cation comprising atleast one positively charged organo-substituted heteroatom; and (ii) acation comprising at least one positively charged heteroatom not part ofan aromatic ring with at least one bond having a bond order greater thanone; and (b) an organic system.
 2. A composition in accordance withclaim 1 wherein said layered mineral is from a kaolinite group,montmorillonite group or illite group.
 3. A composition in accordancewith claim 2 wherein said kaolinite group comprises kaolinite,halloysite, dickite or nacrite.
 4. A composition in accordance withclaim 2 wherein said montmorillonite group comprises montmorillonite,nontronite, beidellite, hectorite or saponite.
 5. A composition inaccordance with claim 2 wherein said illite group comprises hydromicas,phengite, brammallite, glaucomite or celadonite.
 6. A composition inaccordance with claim 1 wherein said layered mineral is kenyaite,magadite, muscovite, sauconite, vermiculite, volkonskoite,phyrophyllics, mica or smectite.
 7. A composition in accordance withclaim 1 wherein said cation in (a) and said cation in (b) comprise aheteroatom selected from the group consisting of N, P, O and S.
 8. Acomposition in accordance with claim 7 wherein said heteroaromaticcation comprising at least one positively charged organo-substitutedheteroatom is an organo-substituted salt of pyrrole, imidazole,thiazole, oxazole, pyridine, pyrimidine, quinoline, isoquinoline,indole, purine, benzimidazole, benzothiazole, benzoxazole, pyrazine,quinoxaline, quinazoline, acridine, phenazine, imidazopyridine ordipyridyl.
 9. A composition in accordance with claim 8 wherein saidorgano-substituted heteroatom is substituted with a C₁₋₂₅ aliphatic,allcyclic or aromatic group.
 10. A composition in accordance with claim8 wherein said heteroaromatic cation is a N-C₁₀₋₁₈ pyridinium cation.11. A composition in accordance with claim 1 wherein said cationcomprising at least one positively charged heteroatom not part of anaromatic ring with at least one bond having a bond order greater thanone has the formula ##STR4## wherein R¹, R², R³ and R⁴ are eachindependently a hydrogen, ##STR5## C₁₋₂₀ alkyl group, aromatic radicalsubstituted heteroatom or and R⁵ is hydrogen or a C₁₋₁₀ alkyl group, orat least one of R¹ and R², R³ and R⁴, R¹ and R³ and R² and R⁴ takentogether with the atoms connecting them form a 4 to 10 membered cyclicor bicyclic ring.
 12. A composition in accordance with claim 11 whereinsaid cation comprising at least one positively charged heteroatom notpart of an aromatic ring is a salt of guanidines or amidines.
 13. Acomposition in accordance with claim 12 wherein said salt of guanidinesis a hexaalkylguanidinium salt.
 14. A composition in accordance withclaim 1 wherein said organic system comprises macrocyclic oligomers,linear polymers or branched polymers.
 15. A composition in accordancewith claim 14 wherein said organic systems are macrocyclic oligomers andselected from the group consisting of macrocyclic polycarbonates,polyesters, polyimides, polyetherimides, polyphenyleneether-polycarbonate oligomers and blends, compositions or co-oligomersprepared therefrom.
 16. A composition in accordance with claim 15wherein said organic systems are linear or branched polymers andselected from the group consisting of polycarbonates, polyesters,polyphenylene ethers, polyimides, olefins, polyetherimides, polyamides,polyarylene sulfides, polysulfones, polyetherketones, acrylonitrilebutadiene styrene copolymers, polystyrenes and blends, compositions andcopolymers prepared therefrom.
 17. A composition in accordance withclaim 16 wherein said polyesters are poly(1,2-ethylene terephthalates),poly(1,4-butylene terephthalates), poly(1,2-ethylene2,6-naphthalenedicarboxylates) or copolymers prepared therefrom.
 18. Acomposition in accordance with claim 16 wherein said polyphenyleneethers comprise homopolymers of 2,6-dimethyl-1,4,-phenylene ether units2,3,6-trimethyl-1,4-phenylene ether units or copolymers preparedtherefrom.
 19. A composition in accordance with claim 16 wherein saidpolycarbonate is a bisphenol A polycarbonate.
 20. A composition inaccordance with claim 1 wherein said composition comprises quartz,brotite, limonite, hydrous micas or feldspar.
 21. A composition which isthe polymerization product of the composition of claim
 15. 22. Acomposition comprising:(a) macrocyclic oligomers; and (b) layeredminerals having undergone a cation exchange with a cation having theformula ##STR6## wherein each R⁶ is independently a hydrogen, C₁₋₂₀alkyl group or substituted or unsubstituted aromatic radical or two R⁶ stogether with atoms connecting them can form a 4 to 12 membered cyclicor bicyclic ring and X is N, P or S and y is an anion.
 23. A compositionin accordance with claim 22 wherein said anion is CI or Br.
 24. Acomposition in accordance with claim 22 wherein said macrocyclicoligomers are selected from the group consisting of macrocyclicpolycarbonates, polyesters, polyimides, polyetherimides, polyphenyleneether-polycarbonate oligomers and blends, compositions and co-oligomersprepared therefrom.
 25. A composition in accordance with claim 24wherein said polyesters are poly(1,2-ethylene terephthalates),poly(1,4-butylene terephthalates), poly(1,2-ethylene2,6-naphthalenedicarboxylates) and copolymers thereof.
 26. A compositionin accordance with claim 24 wherein said polyphenylene ethers comprisehomopolymers of 2,6-dimethyl-1,4-phenylene ether units2,3,6-trimethyl-1,4-phenylene ether units and copolymers thereof.
 27. Acomposition in accordance with claim 24 wherein said polycarbonate is abisphenol A polycarbonate.
 28. A composition in accordance with claim 22wherein said layered mineral is from a kaolinite group, montmorillonitegroup or illite group.
 29. A composition in accordance with claim 28wherein said kaolinite group comprises kaolinite, halloysite, dickite ornacrite.
 30. A composition in accordance with claim 28 wherein saidmontmorillonite group comprises montmorillonite, nontronite, beidellite,hectorite or saponite.
 31. A composition in accordance with claim 28wherein said illite group comprises hydromicas, phengite, brammallite,glaucomite or celadonite.
 32. A composition in accordance with claim 22wherein said layered mineral is kenyaite, magadite, muscovite,sauconite, vermiculite, volkonskoite, phyrophyllics, mica or smectite.33. A method for making a composition comprising layered minerals andpolymerized organic systems comprising the step of adding polymerizationcatalysts to a mixture of:(a) macrocyclic oligomers; and (b) layeredminerals.
 34. A composition which is the polymerization product of thecomposition of claim 22.